Methine compounds

ABSTRACT

Methine compounds useful as fluorescent dyes and pigments are obtained by condensing a 2-phenylbenzazole having at least one amino radical in the benzene group with a 2-methyleneindoline omega - aldehyde.

United States Patent [191 Tanaka Jan. 14, 1975 METHINE COMPOUNDS ToshikiTanaka, Wakayama, Japan Nippon Chemical Works Co., Ltd., Wakayama-ken,Japan Filed: July 28, 1972 App]. No.: 276,263

Inventor:

Assignee:

U.S. C1... 260/240.l, 117/33.5 T, 252/3012 R,

- 260/2408 Int. C1 C07d 55/04 Field of Search 260/2401, 240.8

References Cited UNITED STATES PATENTS 2/1943 Dieterie .Q 95/7 3,311,6193/1967 Fisher et a1. 260/2408 Primary Examiner-G. Thomas Todd Attorney,Agent, or Firm-Eric H. Waters [57] ABSTRACT 13 Claims, N0 DrawingsMETHINE COMPOUNDS This invention relates to novel methine compounds andto processes for production and application thereof.

The novel methine compounds of the present invention can be representedby the general formula,

amino radical; and either one or two of Z Z Z and Z are indolederivatives of the general formula,

wherein B is a substituted or unsubstituted benzene group; R and R,;,which may be same or different, are individually an alkyl group; and Ris an alkyl or substituted alkyl group.

The novel methine compounds of the present invention are particularlyvaluable as colorants such as pigments and dyes, and can be easilyproduced in high yields by condensing a Z-phenylbenzazole having atleast one amino radical in the benzene group with a 2-methyleneindoline-w-aldehyde. The novel compounds thus produced areparticularly strong in fluorescence, have the ability of impartingmarkedly brilliant yellow color tones to natural, artificial andsynthetic materials, can give dyed products extremely high in fastnessparticularly to heat and light, and far more prominent in utility thanthe conventional basic dyes and dye bases corresponding thereto.Accordingly, the novel compounds of the present invention areparticularly useful as colorants when viewed from the industrialstandpoint.

The present invention will be explained in further detail.

In the first place, the process of the present invention is explainedbelow.

The present process can be easily accomplished by subjecting a starting2-phenylbenzazole and one or two equivalents of a starting2-methyleneindoline-waldehyde to condensation reaction in a mineral ororganic acid at normal or elevated temperature. Examples of the startingZ-phenylbenzazole include2-(paminophenyl)-5-methyl-6-aminobenzo-thiazole,2-(paminophenyl)-3,S-dimethylbenzimidazole, aminophenyl)-be'nzimidazole,2-(p-aminophenyl)-5- methoxybenzotriazole, 2-(m-aminophenyl)-6-aminobenzotriazole, 2-(m-amino-p-methoxyphenyl)-6- aminobenzotriazole,.2-(paminophenyl)-5-chloro-6- aminobenzotriazole, aminobenzotriazole,2-(p-amino-m-chlorophenyl)-5- phenyl-6-aminobenzotriazole andZ-(m-amino-pcyanophenyl)-6-aminobenzotriazole, and examples of thestarting 2-methyleneindolinc-w-aldehyde include l,3,3-trimethyl-2-methyleneindoline-w-aldehyde,lcyanoethyl-3,3-dimethyl-2-methyleneindoline-w aldehyde,l-ethyl-3,3-dimethyl-2-methyleneindoline- (J-aldehyde,l,3,3-triethyl-2-methyleneindoline-waldehyde andl,3,3-trimethyl-5-ethylcarbonyl-2- methyleneindoline-w-aldehyde, thoughthese are not limitative.

The mineral acid used in the reaction is desirably hydrochloric orsulfuric acid, and the reaction is ordinarily effected in a 5 to 20 wtpercent aqueous solution, and the organic acid which may be used inplace of the inorganic acid is preferably formic or acetic acid. Ifnecessary, the organic acid may be used in admixture with water or themineral acid. Further, a mixture of two or more compounds correspondingto the abovementioned starting materials may be subjected tocondensation reaction, whereby an optional mixed compound can beobtained according to the aforesaid process. The reaction temperature isordinarily in the range from 10 to 40C., and the reaction time isordinarily in the range from 4 to 8 hours, but these are not limitativeand may be controlled optionally. While the essential conditionsnecessary for practicing the present process are as described in theabove, it would be needless to explain, in view of the ordinary chemicalknowledge, that the product obtained according to the present processmay, of course, be in the form of a basic salt or a zinc chloride doublesalt thereof, or a free base capable of being isolated therefromaccording to a known procedure. 7

In the next place, processes for application of the novel compoundsaccording to the present invention are explained in detail below.

The compounds of the aforesaid general formula have characteristics asbasic dyes and dye bases which are free bases thereof, and hence can beapplied as basic dyes, either as they are or by adoption of variousprocedures, to a variety of materials. For example, not only the presentcompounds in the form of basic dyes can be used, as they are, for thedyeing of cellulose, acrylonitrile, silk, wool and the like fibers, butalso the present compounds in the form of dye bases orpigment-processing dyes can be applied to all such materials aspolyamide, polystyrene, polyurethane, polyvinyl chloride, polyvinylacetal, phenol and the like synthetic resins; leather, wood, paper, pulpand the like natural and artificial materials; and nitrocellulose,acetyl cellulose, ethyl cellulose and the like cellulosic materials,whereby brilliant yellow color tones having strong fluorescencecharacteristics are imparted to the materials. Further, theabove-mentioned dyes or dye bases used in the present processes havesuch characteristic color tones as mentioned above and hence canadvantageously be used in combination with other colorants and the like.Due to their specific properties, the dye bases according to the presentinvention can be used in any forms including water-soluble forms, e.g.in the 2-(p-aminophenyl)-5-methyl-6- form of solutions in water ororganic solvents, in the form of solids or pastes, and in the form ofdispersions. The color tones of materials dyed according to theprocesses of the present invention are yellow to orange colors. When thedyes of the present invention are used in combination with othercolorants, however, various color tones having fluorescencecharacteristics can be imparted to the above-mentioned materials. Thusthe compounds of the present invention are particularly valuable fromthe industrial standpoint.

The present invention is illustrated in more detail below with referenceto examples, in which all parts and percent are by weight.

EXAM PLE 1 21.5 Parts ofl-ethyl-3,3-dimethyl-Z-methyleneindoline-m-aldehyde and 28.1 parts of2-(p-aminophenyl)- 5-diethylaminobenzoxazole are added to 500 parts of 1percent hydrochloric acid, and the resulting mixture is stirred at to C.for about 6 hours to deposit orange color crystals. The depositedcrystals are recovered by filtration, sufficiently washed with a 5percent wool, cotton and the like fibers, and to polyethylene,polystyrene and the like films and sheets to obtain dyed products havingsubstantially the same characteristics as above.

In the case of the dyeing process as mentioned above, various additivesmay, of course, be added as occasion demands.

EXAMPLE 2 aqueous sodium chloride solution and then dried to obtain 47.0parts of a dye powder having the following formula:

H3C\ /CH3 0 2-[{ p-( 6-diethylamino-benz0xazolyl-(2 )-anilino}--ethylenyll-l-ethyl-3,3-dimethylindoline.

Using the thus obtained dye powder, an Orlon cloth (made ofpolyacrylonitrile is dyed according to an ordinary procedure under theconditions of a concentration of 1 percent, a bath ratio of 1:50, atemperature of 95 to 100C. and a time of minutes to obtain a dyedproduct having a brilliant pale yellowish orange color with a strongfluorescence. This dyed product shows such excellent characteristics asa light fastness of 7th grade (JlS, L1044, xenone lamp) and a washingfastness of 5th grade (.118, L1045, MC3).

Procedures identical with or similar to those mentioned above can beapplied also to nylon, acetate, silk,

algaCHME CQNID- C195,5'-Bis{(1,3,3-trimethylindoline-(2-ethylenylamino}-2-phenylbenzotriazole: 0.04'Part of the dye solution is added to aliquor comprising 25 parts of paper-making pulp and parts of water, andthe liquor is stirred for 10 minutes, incorporated with 25 parts of a 2percent rosin liquid and further stirred for additional 5 minutes.Thereafter, 25 parts of a 3 percent aqueous aluminum sulfate solution isadded to the pump liquor to make the total amount 1,500 parts.Subsequently, the pulp liquor is subjected to paper making to, obtain abrilliant yellow colored paper having a strong green fluorescence.

Dye bases having the formulas shown below, which are similar instructure to the above-mentioned dye base, can also be preparedaccording to a process similar to that mentioned above and, when used inthe same manner as above, can impart substantially the same effects asabove to paper-making cellulose pulp.

( l in l l I 6 5,4-Bis{(l ,3,3-trimethylindoline-(2))-ethylenylparts.The resulting deep brown color solution contains -Pk flbqqgtfiggglq 43.0parts of a dye base having the following formula:

CH1 CH: I

cm CH3 eaea CH3 CH1 C H30 NQ- NHCH=CHC EXAMPLE 3 2-[{p-(5-amino-6-methoxybenzotriazolyl-(2))- anilino}-ethylenyl]-l,3,3trimethylindoline.

This solution is extremely stable, and does not change even when it istightly closed in a vessel and allowed to stand at room temperature for6 months.

Using 3 percent of the said solution, an Orlon cloth is dyed in the samemanner as in Example 1 to obtain a A mixture comprising 24.0 parts ofl-cyanoethyl-3,3- dimethyl-2-methyleneindoline-m-aldehyde and 24.6 partsof 2-(p-aminophenyl)-3-methyl-5- chlorobenzimidazole is stirred in 10percent sulfuric acid at room temperature for 8 hours to deposit yellowcrystals. The deposited crystals were recovered by filtration,sufficiently washed with water and ammonia dyed product having abrilll'mt y l wish orange color.

wawr and the dried to obtain 44 pans of a dy6 base The thus obtainedproduct lS substantially identical in having the following formula;fastness with the dyed product obtained in Example 1.

CH3 I CH3 CH3 G3 2-[{ p-( l-methyl-6-chlorobenzimidaZolyl-(2))- EXAMPLE5 anilino}-ethylenyl]-l-cyanoethyl-3,3-dimethylindoline. 10 Parts of thethus obtained dye base is milled in a ball mill for 12 hours, togetherwith 30 parts of a 30 percent aqueous solution of an acrylic acidamidemethacrylic acid amide copolymer, -5 parts of sodiumnaphthalenesulfonate and 55 parts of water, to obtain 100 parts of ayellow aqueous paint having a strong green fluorescence. Using thispaint, leather and wood are colored according to an ordinary procedureto obtain brilliant yellow color products markedly excellent in lightfastness.

50 A mixture comprising 24.0 parts of l-cyanoethyl-3,3-

dimethyl-Z-methyleneindoline-w-aldehyde and 27.4 parts of2-(p-aminophenyl)-5-methyl-6- chlorobenzothiazole is stirred in 100parts of 90 percent a'cetic acid at 40 to C. for 5 hours, and theresulting liquid is gradually dropped into ammonia water to depositorange crystals. The deposited crystals are recovered by filtration,sufficiently washed with water, dried and pulverized to obtain 492 partsof a dye base powder having the following formula:

EXAMPLE 4 on. 'om a; A mixture comprising 20.1 parts of1,3,3-trimethyl-2- S methyleneindoline-w-aldehyde and 25.5 parts of2-(pmo aminophenyl)-5-methoxy-6-aminobenzotriazole is N ICH=CH-C stirredin 60 parts of 50 percent acetic acid at room C1 N% temperature for 6hours, and then ethylene glycol monoethyl ether is added to make thetotal amount CIlzCllzCN aldehyde,

EXAMPLE 6 402 Parts of l,3,3-trimethyl-2-methyleneindoline-w- 1 L partsof 2-(p-aminophenyl)-5- aminobenzotriazole and 12.0 parts of2-(paminophenyl)--amino-6-methylbenzotriazole are subjected tocondensation reaction in the same manner as in Example 2 to obtain adeep brown solution. This so lution contains in a total of 60.0 partssubstantially equal amounts of two dye bases having the followingformulas:

wherein B is a benzene group; A is an oxazole, thiazole, imidazole ortriazole ring fused to the group B; R,, R R and R,, which may be thesame or different, are individually a hydrogen or halogen atom, or aphenyl, alkyl, alkoxy, cyano, amino, or dialkylamino group; and eitherone or two of Z and Z are indole derivatives of the formula, 2

wherein B is a benzene group; R and R which may be the same ordifferent, are individually an alkyl group; and R is an alkyl orcyanoalkyl group; and wherein the alkyl and alkoxy moieties each have 1or 2 carbon atoms.

2. A methine compound of the formula,

0.01 Part of the said solution and 20 parts of an acetic acid solutioncontaining 0.02 part of a dye base Bismark Brown (C.I. No. 21,000) arehomogeneously mixed with each other, and the mixed solution is used totreat paper-making cellulose pulp in the same coloration manner as inExample 2 to obtain a yellowish brown paper product.

What we claim is:

1. A methine compound of the formula wherein R R R and R which may besame or different, are individually a hydrogen or halogen atom, aphenyl, alkyl, alkoxy, cyano, amino or dialkylamino group; R and R whichmay be the same or different, p

are individually an alkyl group; R is an alkyl or cyanoalkyl group; R'is a hydrogen atom or an alkylcarbonyl group; wherein theabove-mentioned alkyl and alkoxy moieties each have 1 or 2 carbon atoms;Y is oxygen, sulfur, NH or a group of the formula NR, where R is a loweralkyl group having 1 to 4 atoms; and X is an equivalent of anion.

3. A free base of the compound described in claim 2.

4. A methinc compound of the formula,

R5 R6 l 6 I R; Ri 1'1 \C-CH=CHNH N e f R4 R2 R1 wherein R,, R R and R,,,which may he the same or are individually an alkyl group; R and R whichmay different, are individually a hydrogen or halogen atom, 10 be thesame or different, are individually an alkyl or cya phenyl, alkyl,alkoxy, cyano, amino or dialkylamino anoalkyl group; R and R which maybe the same or group; R and R which may be same or different, aredifferent, are individually a hydrogen atom or an alkylindividually analkyl group; R is an alkyl group; R is carbonyl group; and X is anequivalent of anion and a hydrogen atom or an alkylcarbonyl group; and Xis wherein the alkyl and alkoxy moieties each have 1 or an equivalent ofanion and wherein the alkyl and alk- 15 2 carbon atoms. oxy moietieseach have 1 or 2 carbon atoms.

A free base of the compound described in claim 7. A free base of thecompound described in claim 6. 6. A methine compound of the formula, 8.

R5 R5 R10 R11 $69 R; N R! R w c CH OH NH N I NH on 011 0 G6 a R9 X N N NI R4 R R1 R12 H3O /0H; 69

c o N(C1II5)2 CCH:CIINIIC J N N lzns X 6 wherein R R R and R which maybe the same or where X is an equivalent of anion. different, areindividually a hydrogen or halogen atom, 9.

H30 /cH cm ea C i C1 C--CII=CHNHC C N N JhClhCN 1 X 6' a phenyl, alkoxy,cyano, amino or dialkylamino group; where X is an equivalent of anion. RR R and R which may be the same or different, 10.

Hick /CH3 ea c s CH:

c-(;ii:(:ii-Nii- I? N 7 3,860,587 11 12 where X is an equivalent ofanion. where X is an equivalent of anion.

c cH=cH N1IC -N\ X NH2 \N/ \N where X is an equivalent of anion. 13.

H3O 01L, eaee 111v 0m N e c c11= :n N11- G9 N N1i i1=011 c X N 41113 N fCII;

12. where X is an equivalent of anion.

1130 CH; ease H3C CH; v N C CCH=CHNH 66 \N NHCI-I:CHC/ X \l 1 11 N N

2. A methine compound of the formula,
 3. A free base of the compounddescribed in claim
 2. 4. A methine compound of the formula,
 5. A freebase of the compound described in claim
 4. 6. A methine compound of theformula,
 7. A free base of the compound described in claim
 6. 8.